Fluorinated carbonates

ABSTRACT

Fluorinated carbonates are described which are useful as miticides. These carbonates often possess herbicidal, insecticidal, and/or fungicidal properties. Examples of the fluorinated carbonates are 2&#39;&#39;, 4&#39;&#39;-dinitro-6&#39;&#39;-secbutylphenyl2,2,2-trifluoroethyl carbonate; 2&#39;&#39;, 4&#39;&#39;-dinitro-6&#39;&#39;-secbutylphenyl-2,2,3,3-tetrafluoropropyl carbonate and 2&#39;&#39;, 4&#39;&#39;dinitro-6&#39;&#39;-cyclohexylphenyl 2,2,3,3-tetrafluoropropyl carbonate.

United States Patent [191 Hardies et al.

[ FLUORINATED CARBONATES [75] Inventors: Donald E. Hardies, Wadsworth; Jay

K. Rinehart, Akron, both of Ohio [H73] AssigneezPPG Industries, Inc., Pittsburgh, Pa.

[22] Filed: Sept. 28, 1970 [21] Appl. No.: 76,275

[52] US. Cl 260/463, 71/106, 424/301 [51] Int. Cl C07c 79/28, AOln 9/20 [58] Field of Search 260/463 [56] 9 References Cited UNITED STATES PATENTS 3,359,296 12/1967 Newallis et al. 260/455 3,234,260 2/1966. Pianka et a1. 260/463 FOREIGN PATENTS OR APPLICATIONS 1,292,937 4/1960 France 1 June 26, 1973 Primary Examiner Lewis Gotts Assistant Examiner-Diana G. Rivers Attorney-Chisholm and Spencer [5 7] ABSTRACT Fluorinated carbonates are described which are useful as miticides. These carbonates often possess herbicidal, insecticidal, and/or fungicidal properties. Examples of the fluorinated carbonates are 2', 4'-dinitro-6'- secbutylphenyl-Z,2,2-trifluoroethyl carbonate; 2, 4'- dinitro-6-sec-butylphenyl-2,2,3,3-tetrafluoropropyl carbonate and 2', 4-dinitro-6-cyclohexy1pheny1 2,2,3,3-tetrafluoropropyl carbonate.

34 Claims, No Drawings l FLUORINATED CARBONATES In accordance with this invention, there are provided carbonates which are effective as miticides and which also often possess herbicidal, insecticidal and/or fungicidal properties.

Carbonates here contemplated may be represented by the formula wherein x is 1, 2 or 3; k is 2, O or 2;

m is an integer ranging from 1 to 15 when k is 2;

m is an integer ranging from 2 to 15 when k is or n is an integer ranging from 1 to (2m+kl); and

R is hydrogen, lower alkyl, halo lower alkyl, lower alkenyl, halo lower alkenyl, lower alkylthio, halo lower alkylthio, lower alkenylthio, halo lower alkenylthio, lower cycloalkyl or halo lower cycloalkyl.

The value for k depends upon the type of bonding in the C,,,H ,,F,, radical. In general, for aliphatic straight or branched chain radicals d is the number of double bonds in the radical, and

t is the number of triple bonds in the radical.

Thus, for aliphatic, straight, or branched chain radicals when k 2 the radical is a fluoroalkyl, when k O the radical is a fluoroalkenyl, and when k 2 the radical is a fluoroalkynyl. Most often, k 2.

R typically contains up to 8 carbon atoms. It ordinarily is a straight or branched lower alkyl group or halo lower alkyl group having 1 to 8 carbon atoms. Often such groups having from 1 to 4 carbon atoms are used. The secondary butyl group is preferred. When R is lower cycloalkyl or halo lower cycloalkyl, it ordinarily contains from 3 to 8 carbon atoms. Most often such groups have from 5 to 8 carbon atoms. Of these cyclic groups, cyclohexyl is preferred.

When R is halo substituted, the halo substituents are usually fluoro, chloro, bromo and/or iodo. Chloro and- /or fluoro are preferred.

The value ofm may range from 1 to or more; however, ranges from 2 to ll or from 3 to ll are more common. When the value ofk is other than 2, m cannot be 1.

While the value of n may range from 1 to (2m+kl n usually ranges from 3 to (2m+kl). Often n is 3 or 4. The value of n is also frequently an even integer ranging from 4 to 20.

The nitro groups and R may be located in any position on the ring. Often the phenyl ring is substituted by two nitro groups. While these groups may be located in any position, it is preferred that they be located in the 2',4'-positions. Although R may be located in any of the 3',5' or 6positions when nitro groups are in the 2,4positions, the preferred location for R is the 6position under such circumstances. When the criteria are met, a class results which may be represented by the following formula:

wherein m is an integer ranging from 1 to 15, more usually ranging from 2 to 11 or 3 to 11;

n is an integer ranging from 1 to (2m+l and R is lower alkyl or halo lower alkyl ordinarily containing from 1 to 8 carbon atoms or cycloalkyl or halo cycloalkyl ordinarily containing from 3 to 8 carbon atoms. When R is lower alkyl or halo lower alkyl, it usually contains from 1 to 4 carbon atoms. When R is cycloalkyl or halo cycloalkyl it usually contains from 5 to 8 carbon atoms. R is preferably secondary butyl or cyclohexyl.

An important class falling within the generic invention is represented by the formula:

(III) wherein x is l, 2 or 3;

i is an integer ranging from 1 to 7, more often ranging from 1 to 5; and

R is lower alkyl or halo lower alkyl ordinarily containing from 1 to 8 carbon atoms or lower cycloalkyl or halo lower cycloalkyl ordinarily containing from 3 to 8 carbon atoms. When R is lower alkyl or halo lower alkyl, it usually contains from 1 to 4 carbon atoms. When R islower cycloalkyl or halo lower cycloalkyl, it usually contains from5 to 8 carbon atoms. R is preferably secondary butyl or cyclohexyl.

The nitro groups and R may be located in any position on the ring. Often the ring is substituted by two nitro groups which are usually in the 2,4-positions while R is usually located in the 6position. This results in the subclass:

(I wherein i is an integer ranging from 1 to 7, more often ranging from I to 5; and R is lower alkyl or halo lower alkyl ordinarily containing from 1 to 8 carbon atoms or lower cycloalkyl or halo lower cycloalkyl ordinarily containing O CO CH C F F ll and 2',4'-dinitro-6-cyclohexylphenyl fluoropropyl carbonate:

2,2,3,3tetra- 0 l odoomcmomn Another important class falling within the generic invention is represented by the formula (VII) wherein x is l, 2 or 3; g is an integer ordinarily ranging from 1 to 14 and,

most often, from 1 to 11 or 4 to 11; and R is lower alkyl or halo lower alkyl ordinarily containing from 1 to 8 carbon atoms or lower cycloalkyl or halo lower cycloalkyl containing from 3 to 8 carbon atoms. When R is lower alkyl or halo lower alkyl, it usually contains from 1 to 4 carbon atoms. When R is lower cycloalkyl or halo lower cycloalkyl, it usually contains from 5 to 8 carbon atoms. R is preferably secondary butyl or cyclohexyl. The nitro groups and R may be located in any position on the ring. Often the ring is substituted by two nitro groups which are usually in the 2,4-positions while R is usually located in the '-position. This results in the subclass:

NO, (VIII) wherein g is an integer ordinarily ranging from i to 14 and,

most often, from 1 to 11 or 4 to ll; and

R is lower alkyl or halo lower alkyl ordinarily containing from 1 to 8 carbon atoms or lower cycloalkyl or halo lower cycloalkyl ordinarily containing from 3 to 8 carbon atoms. When R is lower alkyl or halo lower alkyl, it usually contains from 1 to 4 carbon atoms. When R is lower cycloalkyl or halo lower cycloalkyl, it usually contains from 6 8 carbon atoms. R is preferably secondary butyl or eyclohexyl. of importance is the compound 2',4-dinitro-6-secbutylphenyl 2,2,2-trifluoroethyl carbonate:

CHaCHzCH Still another important class falling within the generic invention is represented by the formula:

(I ooowr mr wherein x is l, 2 or 3;

j is an integer ranging from 1 to 15, more often ranging from 2 to 11 or 3 to ll; and

R is lower alkyl or halo lower alkyl ordinarily containing from 1 to 8 carbon atoms or lower cycloalkyl or halo lower cycloalkyl ordinarily containing from 3 to 8 carbon atoms. When R is lower alkyl or halo lower alkyl, it usually contains from l to 4 carbon atoms. When R is lower cycloalkyl or halo lower cycloalkyl, it usually contains from 5 to 8 carbon atoms. R is preferably secondary butyl or cyclohexyl. I

The nitro groups and R may be located in any position on the ring. Often the ring is substituted by two nitro groups which are usually in the 2,4-positions while R is usually located in the 6'-position. This results in the subclass:

R ma.

wherein j is an integer ordinarily ranging from 1 to 15, more I 1 1 2 ',4',6'-trinitro-3 '-methylphenyl l H, l H,9H-

hexadecafluorononyl carbonate 2 ,4 ,6 -trinitro-3 -methylpheny1 perfluoroheptyl carbonate 3,4,5'-trinitro-2'-methylphenyl 2,2,3,3-tetrafluoropropyl carbonate 3',4',5'-trinitro-2'-sec-butylphenyl l ,2-difluoroethyl carbonate 3',4',5'-trinitro-2-isopropylphenyl eicosafluoroundecyl carbonate These carbonates may be prepared by the reaction of a chloroformate with a substituted phenol. The reaction may conveniently be conducted in a solvent.

Each of Examples 1 XV illustrates a manner in which the contemplated carbonates may be prepared.

EXAMPLE I Phosgene (74 g.) was condensed into anhydrous diethyl ether (200 ml.) contained in a 1 liter, threenecked flask at ice bath temperature. The compound 2,2,2-trifluoroethanol (25.0 g.) in diethyl ether (75 ml.) was added in a stream to the reaction mixture. Anhydrous pyridine (22 g.) in diethyl ether (25 1 ml.) was added drop-wise to the stirred reaction mixture while maintaining a temperature of 4C. to 12C. The dropwise addition of the pyridine was accomplished over a 30-minute period. There was an instantaneous precipitation of pyridine hydrochloride upon addition of the first drop of pyridine. The reaction mixture was stirred for 3 hours while warming to room temperature. The excess phosgene was removed from the reaction mixture under a fine stream of argon. The precipitate pyridine hydrochloride was then removed by filtration and the filtrate distilled under a nitrogen bleed to remove the solvent. Distillation of the residue under a pressure of 165Torr gave the product (17.8 g.) as a colorless liquid. The boiling point of the product was 40C. at 165 Torr. The structure 2,2,2-trifluoroethyl chloroformate was confirmed by nuclear magnetic resonance (NMR) spectroscopy.

Thesodium salt of 2,4-dinitro-6-sec-butyl phenol was prepared by combining 2,4-dinitro-6-sec-butyl phenol (7.9 g.), sodium hydroxide (2.0 g.) and water (150 ml.). Unstabilized methylene chloride (100 ml.) and triethylamine 1 ml.) were then added. The compound 2,2,2-trifluoroethyl chloroformate (4.9 g.) was added dropwise to the vigorously stirred reaction mixture over a 30-minute period while maintaining the temperaturein the range of 24C.-27C. The reaction mixture was stirred for an additional minutes. The two layers were separated and the aqueous layer was washed with methylene chloride (100 ml.). The resulting layers were separated and the organic layer was combined with the organic layer from the first separation. The

combined organic layers were washed with two por-' tions (100 ml. each) of 10% aqueous sodium hydroxide, one portion (100 ml.) of 10% hydrochloric acid and dried over sodium sulfate. The solvent was removed on a rotary evaporator to give 5.4 g. of crude oil which crystallized upon standing. The product was recrystallized from diethyl ether-normal pentane to give 4.2 g. of yellow crystals having a melting point of 9 1C.- -93C. The infrared spectrum showed the carbonate ester absorption at 1782 cm". This product was ana-' lyzed for carbon, hydrogen and nitrogen. The results expressed in per cent by weight are shown in Table l.

TABLE 1 Analysis of 2,4-dinitro-6-sec-butylphenyl 2,2,2-trifluoroethyl carbonate The product may be depicted as having the structural formula:

({)COCH;C F

CH3CH CH N0 EXAMPLE ll Phosgene (74 g.) was condensed into anhydrous diethyl ether (200 ml.) contained in a one liter, threenecked flask at ice bath temperature. The compound 2,2,3,3-tetrafluoro-l-propanol (33.0 g.) in diethyl ether (75 ml.) was added in a stream to the reaction mixture. Anhydrous pyridine (22 g.) in diethyl ether (25 ml.) was added drop-wise to the stirred reaction mixture while maintaining a temperature of 2C. to 8C. The dropwise addition of the pyridine was accomplished over a 20-minute period. There was an instantaneous precipitation of pyridine hydrochloride upon addition of the first drop of pyridine. The reaction mixture was stirred for 3 hours while warming to room temperature. The excess phosgene was removed from the reaction mixture under a fine stream of argon. The precipitated pyridine hydrochloride was then removed by filtration and the filtrate distilled under a nitrogen bleed to remove the solvent. Distillation of the residue under a pressure of 50 Torr gave the product (33.1 g.) as a colorless liquid. The boiling point of the product was 48C.49C. at 50 Torr. The structure 2,2,3,3-tetrafluoropropyl chloroformate was confirmed by NMR spectroscopy.

The sodium salt of 2,4-dinitro-6-sec-butyl phenol was prepared by combining 2,4-dinitro-6-sec butyl phenol (9.6 g.), sodium hydroxide (2.4 g.) and water (150 ml.). Unstabilized methylene chloride ml.) and triethylamine 1 ml.) were then added. The compound 2,2,3,3-tetrafluoropropyl chloroformate (7.8 g.) was added dropwise to the vigorously stirred reaction mixture over a 15-minute period while maintaining the temperature in the range of 25C.29C. The reaction mixture was stirred for an additional l5 minutes. The two layers were separated and the aqueous layer was washed with methylene chloride (100 ml.). The resulting layers were separated and the organic layer was combined with the organic layer from the first separation. The combined organic layers were washed with two portions (100 ml. each) of 10% aqueous sodium hydroxide, one portion (100 ml.) of 10% hydrochloric acid and dried over sodium sulfate. The solvent was removed on a rotary evaporator to give 12.0 g. of crude oil which crystallized upon cooling in ice. The product The results expressed in percent by weight are shown in Table 2.

TABLE 2 Analysis of 2,4-dinitro-6-sec-butylphenyl 2,2,3,3-tetrafluoropropyl carbonate C H N Calculated for ,',H F. N:() 42.22 3.54 7.04 First Analysis 4l .96 3.18 6.96 Second Analysis 42.l l 3.2)

The product may be depicted as having the structural formula:

CI-IaCHzCH NO2 EXAMPLE Ill The sodium salt of 2,4-dinitro-6-cyclohexyl phenol was prepared by combining 2,4-dinitro-6-cyclohexyl phenol (5.3 g.), sodium hydroxide (1.2 g.) and water (150 ml.). Unstabilized methylene chloride (100 ml.) and triethylamine (1 ml.) were then added. The compound 2,2,3,3-tetrafluoropropyl chloroformate (3.9 g.) was added dropwise to the vigorously stirred reaction mixture over a l-minute period while maintaining the temperature in the range of 24C.26C. The reaction mixture was stirred for an additional minutes. The two layers were separated and the aqueous layer was washed with methylene chloride (100 ml.). The resulting layers were separated and the organic layer was combined with the organic layer from the first separation. The combined organic layers were washed with two portions 100 ml.) of 10% aqueous sodium hydroxide, one portion (100 ml.) of 10% hydrochloric acid, and dried over sodium sulfate. The solvent was removed on a rotary evaporator to give 5.0 g. of crude oil which crystallized upon cooling in ice. The product was recrystallized from diethyl ether--normal pentane to give 35 g. of pale yellow crystals having a melting point of 89C.92C. The infrared spectrum showed the carbonate ester absorption at 1780 cm. This product was analyzed for carbon, hydrogen and nitrogen. The results expressed in per cent by weight are shown in Table 3.

TABLE 3 Analysis of 2',4-dinitro-6-cyclohexylphenyl' 2,2,3,3-tetrafluoropropyl carbonate Calculated for m mF4Nz 7 45.29 3.80 6.60 First Analysis 44.99 4.03 6.45

Second Anulysis 45.23 3.88

The product may be depicted as having the structural formula:

EXAMPLE IV The sodium salt of 2,4-dinitro-6-methyl phenol was prepared by combining 2,4-dinitro-6-methyl phenol (4.5 g.), sodium hydroxide (1.3 g.) and water (150 ml.). Unstabilized methylene chloride (1 00 ml.) and triethylamine 1 ml.) were then added. The compound 2,2,3,3-tetrafluoropropyl chloroformate (4.4 g.) was added dropwise to the vigorously stirred reaction mixture over a 25-minute period while maintaining the temperature in the range of 22C.25C. The reaction mixture was stirred for an additional 15 minutes. The two layers were separated and the aqueous layer was washed with methylene chloride (100 ml.). The resulting layers were separated and the organic layer was combined with the organic layer from the first separation. The combined organic layers were washed with two portions (100 ml. each) of 10% aqueous sodium hydroxide, one portion (100 ml.) of 10% hydrochloric acid, and dried over sodium sulfate. The solvent was removed on a rotary evaporator to give 5.4 g. of oil which would not crystallize. The infrared spectrum showed the carbonate ester absorption at 1783 cm. Purity was established as about by NMR spectroscopy.

The product may be depicted as having the structural formula:

EXAMPLE V Phosgene (148.4 g.) was condensed into anhydrous diethyl ether (200 ml.) contained in a one liter, fournecked, round-bottom flask equipped with a dropping funnel, a solid carbon dioxide condenser, a polytetrafluoroethylene blade paddle stirrer, a thermometer, and a phosgene inlet. The compound 1H, 1H, 7l-l-dodecafluoro-l-heptanol (166.1 g.) dissolved in an equal volume of diethyl ether was added in a stream to the mixture. Anhydrous pyridine (43.5 g.) dissolved in an equal volume of diethyl ether was added dropwise to the stirred reaction mixture while maintaining a temperature of 0C. to 10C. The dropwise addition of the pyridine was accomplished over a period of about one hour. The reaction mixture was stirred an additional one hour at 0C. to 10C., then for two hours while gradually warming up to room temperature. The excess phosgene was removed from the reaction mixture under a fine stream of nitrogen. The precipitated pyridine hydrochloride was then removed by i trati eniweehs hd stby s art The diethyl ether wash was squeezed out of the paper into the filtrate. The filtrate was dried with sodium sulfate and diethyl ether solvent was removed by a one-. plate distillation at atmospheric pressure. One-plate distillation of the residue under reduced pressure gave product (180.5 g.) having an assay of 94.9 per cent. The boiling point of the product, 1H, 1H, 7H- dodecafluoroheptyl chloroformate, was 420C. at 1.1 Torr. The sodium salt of 2,4-dinitro-6-sec-butyl phenol was prepared by combining 2,4-dinitro-6-sec-butyl phenol (7.4 g.), sodium hydroxide (1.8 g.), and water (150 ml.). Unstabilized methylene chloride (100 ml.) and triethylamine (1 ml.) were then added. The compound lH, lI-l, 'IH-dodecafluoroheptyl chloroformate (13.0 g.) was added dropwise to the vigorously stirred reaction mixture over a 45-minute period while maintaining the temperature in the range of 22C.25C. The reaction mixture was stirred for an additional 15 minutes. The two layers were separated and the aqueous layer was washed with methylene chloride (100 ml.). The resulting layers were separated and the organic layer was combined with the organic layer from the first separation. The combined organic layers were washed with two portions (100 ml. each) of 10% aqueous sodium hydroxide, one portion (100 ml.) of 10% hydrochloric acid, and dried over sodium sulfate. The solvent was removed on a rotary evaporator to give 15.5 g. of oil which would not immediately crystallize. The'infrared spectrumshowed the carbonate ester absorption at 1780 cm. Purity was established to be about 94 per cent by NMR spectroscopy. The product was analyzed for carbon, hydrogen and nitrogen. The results expressed in per cent by weight are shown in Table 4.

TABLE 4 Analysis of 2', 4-dinitro-6-secbutyl 1H,. 1H, 7H-dodecafluoroheptyl carbonate 7 Calculated for CggHuFrzNzO- 36.13 2.36 4.68 First Analysis 33.84 2.31 6.58 Second Analysis 34.19 2.14 6.58

TABLE 5 Analysis of 2',4-dinitro-6'-sec-butylphenyl 1H, 1H, 7H'dodecafluoroheptyl carbonate C H N First Analysis 35.30 2.46 4.90 Second Analysis 35.15 2.41

The product may be depicted as having the structural formula:

16 ii (?0 OCHflC F 0 FQSEI CH3CH ICH 2 EXAMPLE VI Phosgene (89.0 g.) was condensed into anhydrous diethyl ether (200 ml.) contained in a one liter, fournecked, round-bottom flask equipped with a dropping funnel, a solid carbon dioxide condenser, a polytetrafluoroethylene blade paddle stirrer, a thermometer, and a phosgene inlet. The compound 1H, 1H, 11H- eicosafluoro-l-undecanol (159.6 g.) dissolved in an equal volume of diethyl ether was added in a stream to the mixture. Anhydrous pyridine (26.1 g.) dissolved in an equal volume of diethyl ether was added drop-wise to the stirred reaction mixture while maintaining a temperature of 0C. 10C. The dropwise addition of the pyridine was accomplished over a period of about one hour. The reaction mixture was stirred an additional hour at 0C. 10C., then for two hours while gradually warming up to room temperature. The excess phosgene was removed from the reaction mixture under a fine stream of nitrogen. The precipitated pyridine hydrochloride was then removed by filtration and washed with diethyl ether. The diethyl ether wash was squeezed out of the paper into the filtrate. The filtrate was dried with sodium sulfate and diethyl ether solvent was removed by a one-plate distillation at atmospheric pressure. The solid residue was recrystallized from nhexane, yielding crystals (89.7 g.) having an assay of 78.4 per cent and a melting point of 57.5C.-58.0C. The product was 1H,1H,1 lH-eicosafluoroundecyl chloroformate.

The sodium salt of 2,4-dinitro-6-sec-butyl phenol was prepared by combining 2,4-dinitro-6-sec-butyl phenol (4.8 g.), sodium hydroxide (1.2 g.) and water (150 ml.). Unstabilized methylene chloride-( ml.) and triethylamine (1 ml.) were then added. The-compound 1H,1H,l lfl-eicosafluoroundecyl chloroformate (13.1 g.) was added dropwise to the vigorously stirred reaction mixture over a 35-minute period while maintaining the temperature in the range of 24C.26C. The reaction mixture was stirred for an additional 15 minutes. The two layers were separated and the aqueous layer was washed with methylene chloride 100 ml.). The resulting layers were separated and the organic layer was combined with the organic layer from the first separation. The combined organic layers were washed with two portions (100 ml. each) of 10% aqueous sodium hydroxide, one portion (100 ml.) of 10% hydrochloric acid, and dried over sodium sulfate. The solventwas removed on a rotary evaporator to give 14.1 g. of crude oil which crystallized. The product was recrystallized from diethyl ether--normal pentane to give 6.5 g. of crystals having a melting point of 100.5C.l03C. The infrared spectrum showed the carbonate ester absorption at 1784 cm. This product was analyzed for carbon, hydrogen and nitrogen. The results expressed in per cent by weight are shown in Table 6.

TABLE 6 Analysis of 2'.,4-dinitro 6-sec-butylphenyl 1H, 1H,

1 IH-eicosafluoroundecyl carbonate C H N Calculated for CggHuFzoNzO 33.1 1.77 3.51 First Analysis 32.56 1.94 3.65 Second Analysis 32.61 1.90 Third Analysis 32.41 1.97

The product may be depicted as having the structural formula:

EXAMPLE VII Phosgene (158.3 g.) was condensed into anhydrous diethyl ether (200 ml.) contained in a one liter, fournecked, round-bottom flask equipped with a dropping funnel, a solid carbon dioxide condenser, a polytetrafluoroethylene blade paddle stirrer, a thermometer, and a phosgene inlet. The compound l- (trifluoromethyl)-2,2,2-trifluoroethanol (117.6 g.) dissolved in an equal volume of diethyl ether was added in a stream to the mixture. Anhydrous pyridine (69.6 g.) dissolved in an equal volume of diethyl ether was added dropwise to the stirred reaction mixture while maintaining a temperature of C. to C. The dropwise addition of the pyridine was accomplished over a period of about one hour. The reaction mixture was stirred an additional hour at 0C. to 10C., then for two hours while gradually warming up to room temperature. The excess phosgene was removed from the reaction mixture. The precipitated pyridine hydrochloride was then removed by filtration and washed with diethyl ether. The diethyl ether wash was squeezed out of the paper into the filtrate. The filtrate was dried with sodium sulfate and diethyl ether solvent was removed by a one-plate distillation at atmospheric pressure. Tenplate distillation of the residue at atmospheric pressure gave product (46.4 g.) having an assay of 93 percent. The product was l-trifluoromethyl 2,2,2-trifluoroethyl chloroformate.

The sodium salt of 2,4-dinitro-6-sec-butyl phenol was prepared by combining 2,4-dinitro-6-sec-butyl phenol (8.4 g.), sodium hydroxide (2.1 g.), and water (150 ml.). Unstabilized methylene chloride (100 ml.) and triethylamine (1 ml.) were then added. The compound l-trifluoromethyl)-2,2,2-trifluoroethyl chloroformate (8.3 g.) was added drop-wise to the vigorously stirred reaction mixture over a -minute period while maintaining the temperature in the. range of C.27C. The reaction mixture was stirred for an additional 15 minutes. The two layers were separated and the aqueous layer was washed with methylene chloride (100 ml.) The resulting layers were separated and the organic layer was combined with the organic layer from the first separation. The combined organic layers were washed with two portions (100 ml. each) of 10% aqueous sodium hydroxide, one portion (199 ml.) of 10% hydrochloric acid, and dried over sodium sulfate. The solvent was removed on a rotary evaporator to give 12.4 g. of crude oil which crystallized. The product was recrystallized from diethyl ether-normal pentane to give 8.8 g. of crystals having a melting point of 62.5C.-64.5C. The infrared spectrum showed the carbonate ester absorption at 1795 cm. The product was analyzed for carbon, hydrogen, and nitrogen. The results expressed in per cent by weight are shown in Table 7.

TABLE 7 Analysis of 2',4-dinitro-6'-sec-butylphenyl The product may be depicted as having the structural formula:

a a (I)(,0CHCF3 CHJCIIZICH N03 EXAMPLE VIII The sodium salt of 2-,4-dinitro phenol was prepared by combining 2,4-dinitro phenol (7.3 g.), sodium hydroxide (2.4 g.), and water (150 ml.). Unstablized methylene chloride ml.) and triethylamine (1 ml.) were then added. The compound 2,2,3,3-tetrafluoropropyl chloroformate (8.5 g.) was added dropwise to the vigorously stirred reaction mixture over a 20- minute period while maintaining the temperature in the range of 24.5C.-27.5C. The reaction mixture was stirred for an additional 15 minutes. The 'two layers were separated and the aqueous layer was washed with methylene chloride (100 ml.). The resulting layers were separated and the'organic layer was combined .with the organic layer from the first separation. The combined organic layers were washed with two portions (100 ml. each) of 10% aquous sodium hydroxide, one portion (100 ml.) of 10% hydrochloric acid and dried over sodium sulfate. The solvent was removed on a rotary evaporator to give 11.7 g. of oil which would not crystallize. The infrared spectrum showed the carbonate ester absorption at 1785 cm. Purity was established to be about 92 per cent by NMR spectroscopy.

The product may be depicted as having the structural formula:

0 l .(l) oomomomn EXAMPLE IX The sodium salt of 2,6-dinitro phenol was prepared by combining 2,6-dinitro phenol (7.6 g.), sodium hydroxide (2.4 g.), and water (157.6 ml.). Unstablized methylene chloride 100 ml.) and triethylamine (1 ml.) were then added. The compound 2,2,3,3-tetrafluoropropyl chloroformate (8.5 g.) was added dropwise to the vigorously stirred reaction mixture over a 20- minute period while maintaining the temperature in the range of 25.5C.27.5C. the reaction mixture was stirred for an additional minutes. The two layers were separated and the aqueous layer was washed with methylene chloride (100 ml.) The resulting layers were separated and the organic layer was combined with the organic layer from the first separation. The combined organic layers were washed with two portions (100 ml. each) of 10% aqueous sodium hydroxide, one portion (100 ml.) of 10% hydrochloric acid, and dried over sodium sulfate. The solvent was removed on a rotary evaporator to give 1 1.1 g. of crude oil which crystallized. The product was recrystallized from diethyl ether-normal pentane to give 4.0 g. of crystals having a melting point of 68.5C. 71.5C. The infrared spectrum showed the carbonate ester absorpml.). Unstabilized methylene chloride (100 ml.) and tion at 1790 cm. The product was analyzed for carbon, hydrogen, and nitrogen. The results expressed in per cent by weight are shown in Table 8.

TABLE 8 Analysis of 2',6-dinitrophenyl 2,2,3,3-tetrafluoroprop'yl carbonate The product may be depicted as having thestructural formula:

oiio 011,6 no F,H

EXAMPLE X Phosgene (296.7 g.) was condensed into anhydrous diethyl ether (200 ml.) contained in a one liter, fournecked, round-bottom flask equipped with a dropping funnel, a solidcarbon dioxide condenser, a polytetrafluoroethylene blade paddle stirrer, a thermometer, and a phosgene inlet. The compound 2-fluoroethanol (96.1 g.) dissolved in an equal volume of diethyl ether was added in a stream to the mixture. Anhydrous pyridine (130.5 g.) dissolved in an equal volume of diethyl ether was added dropwise to the stirred reaction mixture while maintaining a temperature of 0C. to 10C. The dropwise addition of the pyridine was accomplished over a period of about one hour. The reaction mixture was stirred an additional hour at 0C. to 10C., then for two hours while gradually warming up to room temperature. The excess phosgene was removed from the reaction mixture. The precipitated pyridine hydrochloride was then removed by filtration and washed with diethyl ether. The diethyl ether wash was squeezed out of the paper into the filtrate. The filtrate was dried with sodium sulfate and diethyl ether solvent was retriethylamine (1 ml.) were then added. The compound 2-fluoroethyl chloroformate (6.9 g.) was added dropwise to the vigorously stirred reaction mixture over a 15-minute period while maintaining the temperature in the range of 27C.-29C. The reaction mixture was stirred for anadditional 15 minutes. The two layers were separated and the aqueous layer was washed with methylene chloride ml.). The resulting layers were separated and the organic layer was combined with the organic layer from the first separation. The combined organic layers were washed with two portions (100 ml. each) of 10% aqueous sodium hydroxide, one portion (100 ml.) of 10% hydrochloric acid and dried over sodium sulfate. The solvent was removed on a rotary evaporator to give 3.3 g. of crude oil which crystallized. The product was recrystallized from diethyl ether-normal pentane to give 1.9 g. of crystals having a melting point of 77.5C.-80.5C. The infrared spectrum showed the carbonate ester absorption at 1772 cm. The product was analyzed for carbon, hydrogen and nitrogen. The results expressed in per cent by weight are shown in Table 9.

TABLE 9 Analysis of 2',4'-dinitro-6-sec-butylphenyl 2-tluoroethyl carbonate C H N Calculated for C10H15FNzO1 47.23 4.58 8.48 First Analysis 47.84 4.91 8.63 47.60 4.84

Second Analysis The product may be depicted as having the structural The sodium salt of 2,4-dinitro-6-tert-butyl phenol was prepared by combining 2,4-dinitro-6-tert-butyl phenol (7.2 g.), sodium hydroxide (1.8 g.), and water ml.). Unstabilized methylene chloride (100 ml.) and triethylamine (1 ml.) were then added. The compound 2,2,3,3-tetrafluoropropyl chloroformate (6.4 g.)

.was added dropwise to the vigorously stirred reaction mixture over a 15-minute period while maintaining the temperature in the range of 23.5C-56.5C. The reaction mixture was stirred for an additional 15 minutes. The two layers were separated and the aqueous layer' was washed with methylene chloride 100 ml.). The resulting layers were separated and the organic layer was combined with the organic layer from the first separation. The combined organic layers were washed with two portions (100 ml. each) of 10% aqueous sodium hydroxide, one portion 100 ml.) of 10% hydrochloric acid, and dried over sodium sulfate. The solvent was removed on a rotary evaporator to give 8.7 g. of crude oil which crystallized. The product was recrystallized from diethyl ethernormal pentane to give 3.5 g. of crystals having a melting point of 88.5C.-9l.5C. The infrared spectrum showed the carbonate ester absorption at 1778 cm". The product was analyzed for carbon, hydrogen and nitrogen. The results expressed in per cent by weight are shown in Table 10.

TABLE 10 Analysis of 2,4'-dinitro-6'-tert-butylphenyl 2.2,3,3-tetrafluoropropyl carbonate The product may be depicted as having the structural formula:

O OOCHlCFzCFIH a l EXAMPLE XII The sodium salt of 2,4-dinitro-6-cyclohexyl phenol was prepared by combining 2,4-dinitro-6-cyclohexyl phenol (12.0 g.), sodium hydroxide (2.7 g.), and water (150 ml.). Unstabilized methylene chloride (100 ml.)

and triethylamine (1 ml.) were then added. The compound 2-fluoroethyl chloroformate (6.2 g.) was added dropwise to the vigorously stirred reaction mixture over a 25-minute period while maintaining the temperature in the range of 25C.27C. The reaction mixture was stirred for an additional 15 minutes. The two layers were separated and the aqueous layer was washed with methylene chloride (100 ml.). The resulting layers were separated and the organic layer was combined with the organic layer from the first separation. The combined organic layers were washed with two portions (100 ml. each) of 10% aqueous sodium hydroxide, one portion (100 ml.) of 10% hydrochloric acid, and dried over sodium sulfate. The solvent was removed on a rotary evaporator to give 8.8 g. of crude oil which crystallized. The product was recrystallized from diethyl ether-normal pentane to yield 4.0 g. of crystals having a melting point range of 110.5C. to 115.5C. The infrared spectrum showed the-carbonate ester absorption at 1772 cm. The product was analyzed for carbon, hydrogen and nitrogen. The results expressed in per cent by weight are shown in Table 11.

TABLE 1 1 Analysis of 2,4'-dinitro-6-cyclohexylphenyl 2-fluoroethyl carbonate g The product may be depicted as having the structural formula:

EXAMPLE XIII The sodium salt of 2,4-dinitro-6-cyclohexyl phenol was prepared by combining 2,4-dinitro-6-cyclohexyl phenol (9.3 g.), sodium hydroxide (2.1 g.), and water (150 ml.). Unstabilized methylene chloride ml.)

'an d triethylamine (1 'ml.) were then added. The compound l-(trifluoromethyl)-2,2,2-trifluoroethyl chloroformate (8.8 g.) was added dropwise to the vigorously stirred reaction mixture over a 28-minute period while maintaining the temperature in the range of 25.5C.-28C. The reaction mixture was stirred for an additional 15 minutes. The two layers were separated and the aqueous layer was washed with methylene chloride 100 ml.). The resulting layers were separated and the organic layer was combined with the organic layer from the first separation. The combined organic layers were washed with two portions (100 ml. each) of 10% aqueous sodium hydroxide, one portion (100 ml.) of 10% hydrochloric acid, and dried over sodium sulfate. The solvent was removed on a rotary evaporator to give 8.3 g. of crude oil which crystallized. The

TABLE 12 Analysis of 2,4'-dinitro-6-cyclohexylphenyl -1-(trifluoromethyl)-2,2,2-trifluoroethyl carbonate Calculated for CIGHHF6N207 41.75 3.07 6.09 Found W 41.5 2.86 6.13

The product may be depicted as having the structural mul o 01 (lMi JOJlHCFa EXAMPLE XIV The sodium salt of 2,4-dinitro-6-cyclohexyl phenol was prepared by combining 2,4-dinitro-6-cyclohexyl phenol (7.0 g.), sodium hydroxide (1.6 g.), and water (150 ml.). Unstabilized methylene chloride (100 ml.) and triethylamine (1 ml.) were then added. The compound lH,IHJH-dodecafludroheptyl chloroformate (l 1.0 g.) was added drop-wise to the vigorously stirred reaction mixture over a 30-minute period while maintaining the temperature in the range of 24.5C.-26.5C. The reaction mixture was stirred for an additional 15 minutes. The two layers were separated and the aqueous layer was washed with methylene chloride (100 ml.). The resulting layers were separated and the organic layer was combined with the ogranic layer from the first separation. The combined organic layers were washed with two portions (100 ml. each) of 10% aqueous sodium hydroxide, one portion (100 ml.) of 10% hydrochloric acid and dried over sodium sulfate. The solvent was removed on a rotary evaporator to give 14.4 g. of crude oil which crystallized. The product was recrystallized from diethyl ether--normal pentane to yield 6.5 g. of crystals having a melting point range of 68.5C. to 72C. The infrared spectrum showed the carbonate ester absorption at 1780 cm". The product was analyzed for carbon, hydrogen and nitrogen. The

results expressed in per cent by weight are shown in Table 13.

TABLE 13 Analysis of 2,4'-dinitro-6'-cyclohexylphenyl 1H, 1H, 7H-dodecafluoroheptyl carbonate The product may be depicted as having the structural formula:

ll 0 c0 011 a: no F0111 @O NO:

EXAMPLE XV The sodium salt of 2,4-dinitro-6-cyclohexyl phenol was prepared by combining 2,4-dinitro-6-cyclohexyl phenol (5.3 g.), sodium hydroxide (l.2 g.) and water (150 ml.). Unstabilized methylene chloride (100 ml.) and triethylamine (1 ml.) were then added.'The compound lH,lH,l lH-eicosafluoroundecyl chloroformate 13.0' g.) was added drop-wise to the vigorously stirred reaction mixture over a 25 minute period while maintaining the temperature in the range of 24C.25C. The reaction mixture was stirred for an additional 15 minutes. The two layers were separated and the aqueous layer was washed with methylene chloride (100 ml.). The resulting layers were separated and the organic layer was combined with the organic layer from the first separation. The combined organic layers were washed with two portions 100 ml. each) of 10% aqueous sodium hydroxide, one portion (100 ml.) of l0% hydrochloric acid and dried over sodium sulfate. The

solvent was removed on a rotary evaporator to give 9.6

. g. of crude oil which crystallized. The product was re- TABLE 14 Analysis of 2',4-dinitro-6'-cyclohexylphenyl 1H, 1H, 1 lH-eicosafluoroundecyl carbonate Calculated for C124 H 16 2flN2 7 Found The product may be depicted as having the structural formula:

1? poootmonc F0511 Many of the fluorinated alcohols used to prepare the precursor chloroformates and many of the substituted phenols are known to the art. In those instances where the compounds having the desired substitutions are not available, they may be prepared by any of the methods well known in chemistry. In the case of compounds falling within the scope of formula (ill) a particularly advantageous method is available for preparing the precursor alcohol which consists in reacting methanol with one or more equivalents of tetrafluoroethylene in the presence of a free radical initiator. The over-all equation for the reaction is:

More specific details of this reaction may be found in U. S. Pat. Nos. 2,959,611 and 2,559,628. The l,ldihydroperfluoroalkyl alcohols and their preparation are described in U. S. Pat. No. 2,666,797. The reaction between fluoro alcohols and phosgene to form chloroformates is described in U. S. Pat. No. 2,959,611. The preparation of perfluoroalkyl chloroformates from perfluoroalkyl hypochlorites is described by Young et al., Perfluoroalkyl Chloroformates and Chlorosulfates, Tetrahedron Letters, N0. 9 1969) Pergamon Press, pp. 723-726. The fluorinated alkenyl chloroformates and fluorinated alkynyl chloroformates may be prepared by methods analogous to those for preparing the fluorinated alkyl chloroformates.

ln general, the carbonates of this invention may be used to kill or retard development of mites.

In one embodiment the carbonate is applied directly to the mites. In another embodiment the carbonate is applied to regions where mites are likely to be found in order to kill the mites present or to preclude mite populations from becoming established.

Usually formulations containing from about to about 2,000 parts per million by weight (ppm) of the carbonate compound are applied. Typical formulations contain from about to about 1,000 ppm. Often formulations containing from about 10 to about 100 ppm are used.

The type of formulation used may vary. Solutions and suspensions of the carbonate are effective. The usual method of applying solutions or suspensions is to drench the area of application. Sprays, showers, mists, and dips may be used for this purpose. When some of the more active carbonates are used, particularly at higher concentrations, a complete drenching is not necessary. Mists are often used where a drench is not desired.

The carbonate formulations of the invention may also be applied in the form of a powder or dust. These powders or dusts may contain diluents such as, for example, aluminum silicate, bentonite, calcium carbonate, calcium silicate, diatomaceous silica, hydrated lime, pulverized limestone, montmorillonite, pulverized phosphate rock, silica, talc, or vermiculite.

The concentration of the carbonate compound in the formulation and the total amount applied will vary depending upon the particular carbonate being employed and the particular mite being confronted. Other factors such as season of the year, environmental conditions, and stage of mite development all have their effect.

The following specific embodiments illustrate, by way of example, the basic principles of the present invention:

EXAMPLE XVI Potted horticultural bean plants (Phaseolus vulgaris, L.) at growth stage when primarily leaves are approximately I inch long are infested with two-spotted spider mites (Tetranychus urticae) 24 hours prior to treatment, insuring establishment of adults and deposition of eggs at the time of treatment.

When possible, the test compounds are formulated as follows: A stock acetone emulsion is prepared having the following composition by weight: 99.75 per cent ac-' etone, 0.20 per cent sorbitan trioleate (Span 85), and 0.05 per cent sorbitan monooleate polyoxyalkylene derivative (Tween 80). Test compound is dissolved in a portion of the stock acetone emulsion. Deionized water is added to yield a concentrated test solution containing about 10 per cent acetone, 0.020 percent Span 85 and 0.0050 per cent Tween 80. The amount of test compound dissolved in the stock acetone emulsion is such that when diluted with deionized water the concentrated test solution has the highest concentration (usually 1,000 ppm) of test compound used in the tests. Other solutions are prepared by diluting the concentrated test solution with a mixture of deionized water and stock acetone emulsion, which mixture contains about 10 per cent acetone, 0.020 per cent Span 85, and 0.0050 per cent Tween 80. Thus, all test solutions always contain about 10 per cent acetone, 0.020 per cent Span 85, and 0.0050 per cent Tween 80, irrespective of the concentration of test compound. Compounds giving an unsatisfactory formulation as an acetone emulsion are formulated as wet-table powders and diluted with water and wetting agent before application.

Infested host plants are dipped into agitated solutions of the test compound, allowed to air dry, provided with bonate.

TABLE 15 Miticidal Effectiveness of 2,4-Dinitro-6-sec-butylphenyl 2,2,2-Trifluoroethyl Carbonate Against Two-Spotted Spider Mite (Tetranychus urticae) Concentration Per Cent Mortality ppm Initial Ovicidal Residual L000 I00 100 No Young 500 I00 90 I00 250 100 99 100 75 0, Trace, 83 94, Trace 50 0, 48 0 25 ij 0, 20 0 EXAMPLE xvn The procedure of Example XVI is repeated except that the test compound is 2',4-dinitro-6'-secbutylphenyl 2,2,3,3-tetrafluoropropyl.carbonate. Table 16 reports the observed results of this test.

TABLE 16 Miticidal Effectiveness of 2',4-Dinitro-6'-butylphenyl 2,2,3,3-Tetrafluoropropyl Carbonate Against Two-Spotted Spider Mite (Tetranychus urticae) Concentration Per Cent Mortality ppm Initial Ovrcrdal Residual 1,000 lOO I00 N0 Young 500 I00 100 No Young 250 I00 I00 No Young I00 100 I0 0 50 I00 25 I00 l0 4| EXAMPLE XVIII The procedure of Example XVI is'repeated except that the test compound is 2,4-dinitro-6'- cyclohexylphenyl 2,2,3,3-tetrafluoropropyl carbonate. Table 17 reports the observed results of this test.

TABLE 17 Miticidal Effectiveness of 2,4-'Dinitro-6-cyclo-hexylphenyl 2,2,3,3,-Tetrafluoropropyl Carbonate Against Two-Spotted Spider Mite (Tetranychus urticae) Concentration Per Cent Mortality ppm Initial Ovicidal Residual l .000 88 Trace 90 50 24 0 0 25 5 0 0 l0 8 0 0 EXAMPLE XIX The procedure of Example XVI is repeated except that the test compound is 2',4'-dinitro-6'-methylphenyl 2,2,3,3-tetrafluoropropyl carbonate. Table 18 reports the observed results of this test.

TABLE I8 Miticidal Effectiveness of 2,4'-Dinitro-6'-methylphenyl 2,2,3,3-Tetrafluoropropyl Carbonate Against Two-Spotted Spider Mite (Tetranychus urticae) Concentration Per Cent Mortality ppm initial Ovicidal Residual EXAMPLE XX The procedure of Example XVI is repeated except that the test compound is 2',4-dinitro-6'-secbutylphenyl I H, l I-I,I 1H-eicosafluoroundecyl carbonate. Table 19 reports the observed results of this test.

TABLE I9 Miticidal Effectiveness of 2',4'-Dinitro- 6'-sec-butylphenyl 1H, 1H, llH-Eicosafluoroundecyl Carbonate Against Two-Spotted Spider Mite Tetranychus urticae) Concentration Per Cent Mortality ppm Initial Ovicidal 1,000 97 0 500 87 25 250 25 Trace I00 19 0 EXAMPLE XXI The procedure of Example XVI is repeated except that the test compound is 2,4'-dinitro-6-secbutylphenyl l-(trifluoromethyI)-2,2,2-trifluoroethyl carbonate. Table 20 reports the observed results of this test.

TABLE 20 Miticidal Effectiveness of 2,4'-Dinitro-6'-sec-butylphenyl I -(Trifluoromethyl )-2,2,2-trifluoroethyl Carbonate Against Two-Spotted Spider Mite (Tetranychus EXAMPLE XXII The procedure of Example XVIis repeated except that the test compound is 2',4'-dinitrophenyl 2,2,3,3-tetrafluoropropyl carbonate. Table 21 reports the observed results of this test. TABLE 21 Miticidal Effectiveness of 2,4'-Dinitrophenyl 2,2,3,3,-Tetrafluoropropyl Carbonate Against Two-Spotted Spider Mite (Tetranychus urticae) Per Cent Mortality Initial Ovicidal Concentration 80 Trace 0 EXAMPLE XXIII The procedure of Example XVI is repeated except that the test compound is 2,6'-dinitrophenyl 2,2,3,3-tetrafluoropropyl carbonate. Table 22 reports the observed results of this test.

TABLE 22 Miticidal Effectiveness of 2',6'-Dinitrophenyl 2,2,3,3-Tetrafluoropropyl Carbonate Against Two-Spotted Spider Mite (Tetranychus urticae) Concentration Per Cent Mortality Initial Ovicidal EXAMPLE XXIV The procedure of Example XVI is repeated except tht the test compound is 2',4'-dinitro-6'-secbutylphenyl 2-fiuoroethyl carbonate. Table 23 reports the observed results of this test.

TABLE 23 Miticidal Effectiveness of 2',4-Dinitro-6-sec-butylphenyl 2-Fluoroethyl Carbonate Against Two-Spotted Spider Mite Tetranychus um'cae) 3 5 Per cent Mortality Initial Ovicidal Concentration I00 I00 I00 I00 85 30 8 EXAMPLE XXV The procedure of Example XVI is repeated except that the test compound is 2',4-dinitro-6'-tertbutylphenyl 2,2,3,3-tetrafluoropropyl carbonate. Table 24 reports the observed results of this test.

TABLE 24 Miticidal Effectiveness of 2,4-Dinitro-6-tert-butylphenyl 2,2,3,3-Tetrafluoropropyl Carbonate Against Two-Spotted Spider Mite (Tetranychus urticae) Concentration Per Cent Mortality Initial Ovicidal I00 Trace 0 EXAMPLE XXVI The procedure of Example XVI is repeated except that the test compound is 2,4-dinitro-6-secbutylphenyl l H, l I-IJH-dodecafluoroheptyl carbonate. Table 25 reports the observed results of this test.

Concentration Per cent Mortality ppm Initial Ovicidal l .000 100 45 500 100 70 250 100 30 100 53 Trace Many of the carbonates of the present invention possess properties which make them useful as phytocides, as for example, herbicides. Weeds may be killed by applying to the soil in the vicinity of the weeds a phytocidal amount of the carbonate. Weeds may also be killed by bringing a phytocidal amount of the carbonate and the weeds into mutual contact, as for example, by applying the carbamate directly to the weeds. In another embodiment the carbonate is applied to the solid where weeds are likely to be found in order to preclude weeds from becoming established.

The formulations used as phytocides are similar in all material respects to those described above for miticidal purposes. The concentration of the carbonate compound in the formulation and the total amount applied will vary depending upon the particular carbonate being employed and the particular weed being confronted. Other factors such as season of the year, environmental conditions and stage of weed development all have their effect. Exemplary application rates are from about 0.1 to about 100 pounds per acre. Usually the rate will change from about 0.1 to about 20 pounds per acre. Rates of from about 0.5 to about pounds per acre are most often used.

In Examples XXVII through Ll the following procedure was used: For pre-emergence testing, appropriate weed species are seeded in individual disposable threeinch square containers containing about 2 inches of soil. After spraying directly on the seeded soil surface, a small amount of sand, usually about /8 to A inch in depth, is applied to cover the seeds.

For post-emergence testing, appropriate weed species are seeded by growth-time requirement schedules in individual disposable 3 inch square containing containers about 2 inches of soil, watered as required, and maintained under greenhouse conditions. When all weeds have reached suitable growth development, generally first true leaf stage, plants appropriate to pertaining test requirements are selected for uniformity of growth and development. One container of each weed, averaging up to 50 plants per individual container, is then placed on a carrying tray for treatment.

When possible, the test compounds are formulated in a solvent mixture of 90 percent acetone, 8 percent ethanol, and 2 percent dimethylformamide by volume. Insoluble compounds are formulated as wettable powders and diluted with water and wetting agent before application.

Each carrying tray of pre-emergence and/or post emergence containers, placed on a conveyor belt having a linear speed of 1.5 miles per hour, trips a microswitch which, in turn, activates a solenoid valve and releases the compound under test. The compound under test is discharged as sprays at a rate of 50 gallons per acre. Containers for both pre-emergence and postemergence testing are then removed to the greenhouse and held for observation.

Pre-emergence and post-emergence treatments are observed daily for interim response, final observations usually being made 14 days after treatment. Any treatments inducing significant response are held beyond the 14-day observation period until such responses can be confirmed. Each result is reported as an Injury Rating which is represented as follows: 0 no visible effect; 1, 2, 3 slight injury, plant usually recovered with little or no reduction in top growth; 4, 5, or 6 moderate injury, plants usually recovered but with reduced top growth; 7, 8, or 9 severe injury, plants usually did not recover; 10 all plants killed. Deviations from the above procedure, if any, are reported with the data.

EXAMPLE XXVll Test Compound: 2',4'-Dinitro-6'sec-butylphenyl J ohnsongrass (Sorghum halepense Pers.) l 3 Lambsquarter (Chenopodium album L.) l0 Mustard (Brassica kaber L. C. Wheeler Var.

pinnalxflda L. C. Wheeler) l0 l0 Yellow Foxtail (Selaria glauca Beauv.) O 0 Barnyardgrass (Echinochloa crusgalli Beauv.) l 2 Crabgrass (Digilaria sanguinalis Scop.) 2 3 Buckwheat (Polygonum convulvulus L.) 9 10 Morning Glory (mixture of Ipomoea purpurea Roth and lpomoea hederacea .lacq.) 8 10 Red Kiney Bean (Phaseolus vulgarir L.) Untreated Controls 3 Normal Normal EXAMPLE XXVlll Test Compound: 2',4'-Dinitro-6-sec-butylphenyl 2,2,2-trifluoroethyl carbonate Observations made 16 days after application Pre-Emergence Test Plant 5 2.5 1.25 lb/A lb./A lb/A Yellow Nutsedge (Cyperus esculentus L.) 0 0 0 Wild Oats (Avena fafus L.) 1 O O Jimsonweed (Datura :tramonium L.) 9 8 8 Velvetleaf (Abutilan theophrasli Medic.) 9 8 0 Johnsongrass (Sorghum halepense Pers.) 0 0 0 Lambsquarter (Chenopodium album L.) l0 l0 l0 Mustard (Brassiva kaber L. C.

Wheeler Var. Pinnatiflda L. C. 'Wheeler) l0 l0 9 Yellow Foxtail (Setaria glauca Beauv.) 2 0 0 Barnyardgrass (Echinochloa crusgalli Beauv.) 3 O Crabgrass (Digitaria sanguinalis Scop.) 2 0 0 Buckwheat (Polygonum convolvulus L.) I 9 9 9 Morning Glory (mixture of Ipomoea purpurea Roth and lpamoea hederace Jacq.) 2 4 l Untreated Controls Normal. Normal Normal EXAMPLE XXIX Test Compound: 2',4'-Dinitro6'-sec-butylphenyl 2,2,2-trifluoroethyl carbonate Observations made 2l days after appliation Pre-Emergence 2.5 lb/A 1.25 lb/A Normal Normal Test Compound: 2',4'-Dinitro-6-sec-butylphenyl 2,2,2-trifluoroethyl carbonate Observations made 13 days after application Test Plant Yellow Nutsedge (Cyperus esculenlus L.)

Wild Oats (Avena farua L.)

.limsonweed (Datum slramom'um Velvetleaf (Abuiilon lheoprasti Medic.)

Johnsongrass (Sorghum halepmre Pers.)

Mustard (Brassica kaber L. C.

Wheeler Var. pinnarifida L. C. Wheeler Yellow Foxtail (Setarr'a glam-a Beauv.)

Barnyardgrass (Echinochloa crusgalli Beauv.

Crabgrass (Digitaria .ranguinah's Scop.)

Buckwheat (Polygonum canvolvulus L.)

Morning Glory (mixture of Ipomoea purpurea Roth and lpomoea hederacea Jacq.)

Red Kidney Bean (Phaseolus vulgaris L.)

Primary Leaf Stage Triloliate Leaf Stage Untreated Controls Post-Emergence 0 l Normal EXAMPLE XXXI 2.5 lb/A Normal Normal Test Compound: 2, 4'-Dinitro-6-sec-butylphenyl 2,2,3,3-tetrafluoropropyl carbonate Pre-Emergence Observations made 21 days after application.

Post-Emergence Observations made 9 days after application.

Test Plant Yellow Nutsedge (Cyperu: ercqlenrus L.) Wild Oats (Avem; fatua L.) Jirnsonweed (Datum srmmonium L.) Velvetleaf (Abulilon lheophrasti Medic.) Johnsongrass (Sorghum halepense Pers.) Lambsquarter (Chmwpodium album L.) Mustard (Brassica kaber L. C. Wheeler Var.

pinmzrifida L. C. Wheeler) Yellow Foxtail (Setaria glauca Beauv.) Barnyardgrass (Echinochloa crusgalli Beauv.) Crabgrass (Dr'gr'tnria sanguinalis Scop.) Buckwheat (Polygonum convolvulus L.) Morning Glory (mixture of lpamoea purpurea Roth and Ipomoea hederacea Jacq.) Red Kidney Bean (Phaseolus vulgaris L.) Untreated Controls EXAMPLE XXX" Pre- Emergence Normal Post- Emergence Normal Test Compound: 2',4-Dinitro 6'-sec-butylphenyl 2,2,3,3-tetrafluoropropyl carbonate Observations made 16 days after application Test Plant Yellow Nutsedge (Cyperu;

esculenrus L.)

Wild Oats (Avena form: L.)

J imsonweed (Datum .flramom'um Velvetleaf (Abutilon rheophmrri Medic.) .lohnsongrass (Sorghum halepenre Pers.) Lambsquarter (Chenopodium album L.) l0 Mustard (Brassica kaber L. C.

Wheeler Var. pinnatxfida L. C.

Wheeler) l0 Yellow Foxlail (Seran'a glauca Beauv.) 2 Barnyardgrass (Echinochloa crusgalli Beauv.) 2 Crabgrass (Digilaria sanguirmlr's Scop.) 3 Buckwheat (Polygonum convalvulus L.) 8 Morning Glory (mixture of lpomoea purpurea Roth and Ipomoea hederacea Jacq.) 5 Untreated Controls Normal EXAMPLE XXXllI Pre- Emergence 1 Normal l Normal Test Compound: 2,4' Dinitro-6'-sec-butylphenyl I '2,2,3,3-tetrafluoropropyl carbonate Observations made 2i days after application Test Plant lb/A Yellow Nutsedge (Cyperus esculenms L.) 0 Wild Oats (Avena fatua L.) O Jimsonweed (Datum .rrramonium L.) 10 Velvetleaf (Aburilon rheaphrarli Medic.) 9 Johnsongrass (Sorghum haiepense Pers.) 0 Lambsquarter (Chenopodrum album L.) 10

Mustard (Brassica kaber L. C.

Wheeler Var. pinnatijida L. C.

Wheeler) l0 Yellow Foxtail (Sezaria glauca Beauv.) 0 Barnyardgrass (Echinochloa crusgalli Beauv.) 2 Crabgrass (Digimria sanguinah's Scop.) 2 Buckwheat (Polygonum convolvulus L.) 10

Morning Glory (mixture of lpomoea purpurea Roth and Ipomoea hederacea .lacq. 4 Untreated Controls Normal Pre-Emergence 5 2.5 lb/A 1.25 lb/A OOOGOO 2 Normal Normal EXAMPLE xxxiv Test Compound: 2',4'-Dinitro-6'-sec-butylphenyl 2,2,3,3-tetrafluoropropyl carbonate Observations made 13 days after application Post-Emergence Test Plant 5 lb/A 2-.5 lb/A 1.25 lb/A Yellow Nutsedge (Cyperus erculemus L.) 2 0 0 Wild Oats (Avena fatua L.) 8 6 4 Jimsonweed (Datum smzmonium L.) l0 l0 l0 Velvetleaf (Abutilon theophrasti Medic.) l0 l0 l0 Johnsongrass (Sorghum halepense Pets.) 3 l 0 Mustard (Brassica kaber L. C.

Wheeler Var. pinnaufida L. C.

Wheeler) l0 l0 Yellow Foxtail (Semria glauca Beauv.) l l 0 0 Bamyardgrass (Echinochloa crusgalli Beauv.) 8 4 2 Crabgrass (Digilaria .ranguinalis Scop.) l 0 0 Buckwheat (Polyganum convolvulus L.) l0 l0 10 Morning Glory (mixture of lpomoea purpurea Roth and lpomoea hederacea .lacq.) l0 l0 9 Red Kidney Bean (Phaseolus vulgaris L.)

Primary Leaf Stage 1 0 0 Trifoliate Leaf Stage 0 0 0 Untreated Controls Normal Normal Normal EXAMPLE XXXV Test Compound: 2',4-Dinitro-6'-cyclohexylphenyl 2,2,3,3-tetrachloropropyl carbonate Pre-Emergence Observations made 13 days after application Post-Emergence Observations made 14 days after application Post- Emergence l0 lbJA Pre- Emergence l0 lb./A

, Test Plant Yellow Nutsedge (Cyperus esculentus L.) Wild Oats (Avena fatua L.) Jlmsonweed (Darura slramonium L.) Velvetleaf (Abutilon theophrasti Medic.) .lohnsongrass (Sorghum halepense Pers.) Pigweed (Amaranthus retroflexus L.) Mustard (Brassica kaber L. C. Wheeler Var.

pinnatifida L. C. Wheeler) Yellow Foxtail (Setaria gIauca Beauv.) Barnyardgrass (Echinochloa crusgalli Beauv.) Crabgrass (Digitaria sanguinalis Scop.) Buckwheat (Polyganum canvolvulu: L.) Morning Glory (mixture of Ipomoea purpurea Roth and Ipomoea hederacea Jacq.) Red, Kidney Bean (Pharealu: vulgaris L.)

Primary Leaf Stage Trifoliate Leaf Stage Untreated Controls 0 ooooq \OOOOOO o OOONO Normal Norm EXAMPLE XXXVI Test Compound: 2',4-Dinitro-6-methylphenyl 2,2.3,3-'tetrafluoropropyl carbonate Pro-Emergence Observations made 13 days after Pigweed (Amaranthu: relroflexus L.) Mustard (Brassica kaber L; C. Wheeler Var.

pinnnnfida L. C. Wheeler) Yellow Foxtail (Setaria glauca Beauv.) Barnyardgrass (Echinochloa crusagalli Beauv.) Crabgrass (Digimria sanguinalis Scop.) Buckwheat (Palygonum convolvulus L.) Morning Glory (mixture of lpomaea purpurea Roth and Ipomoea hederacea Jacq.) Red Kidney Bean (Phoseolus vulgaris L.)

lsPrimary-Leaf Stage Trifoliate Leaf Stage Untreated Controls O) AUONW EXAMPLE XXXVI! Test Compound: 2';4'-Dinitro-6'-methylphenyl 2,2,3,3-tetrafluoropropyl carbonate Observations made 21 days after application Pre- Test Plant Emergence 5 Fire utocuc coca-o EXAMPLE XXXVIII Test Compound: 2,4'-Dinitro-6 -sec-butylphenyl l H, l H, l lH-eicosafluororoundecyl carbonate Observations made 13 days after application (left column) Observations made 23 days after application (right column) Pre-Emergence Test Plant 10 lb./A 10 Yellow Nutsedge (Cyperus esz'ulemus L.) 0 0 Wild Oats (Av'emz farua L.) 0 0 Jimsonweed (Datum stramom'um L.) 8 8 Velvetleaf (Abutilon theophrasti Medic.) 6 4 Johnsongrass (Sorghum halepense Pers.) 0 0 Pigweed (Amaranlhus relroflexus L.) l0 8 Mustard (Brarsica kaber L. C. Wheeler Var.

. pinnanfida L. C. Wheeler l0 10 Yellow Foxtail (Setaria glaucn Beauv.) 9* 9" Barnyardgrass (Echinochloa crusgalli Beauv.) 3 2 Crabgrass (Digitaria sanguinqlis Scop.) 3 0 Buckwheat (Polygonum convolvulus L.) 3 0 Morning Glory (mixture of Ipomaea purpurea Roth and Ipomoea hederacea Jag: 2 l Untreated Controls *Possible bird damage. Normal Normal EXAMPLE XXXIX Test Compound: 2,4-Dinitro-6'-sec-butylphenyl l H, 1H, 1 lH-eicosafluoroundecyl carbonate Observations made 12 days after application Post- Test Plant Emergence l0 lbJA Yellow Nutsedge (Cyperus esculentus L.) 0 Wild Oats (Avena fatua L.) O .limsonweed (Darura :tramom'um L.) '8 Velvetleaf (Abutilon theophrasli Medic.) 0 Johnsongrass (Sorghum halepense Pers.) 0 Mustard (Brassica kaber L. C. Wheeler Var.

pinmmfida L. C. Wheeler) 0 Yellow Foxtail (Selaria glauca Beauv.) O Barnyardgrass (Echinochloa crusgalli Beauv.) O Buckwheat (Polygonum convolvulus L.) 9

Normal Normal Morning Glory (mixture of Ipomoea purpurea Roth and Ipomoea hedemcea Jacq.) Red Kidney Bean ('Phaseolus vulgaris L.) 0 Untreated Controls Normal EXAMPLE XL Test Compound: 2,4'-Dinitro-6-sec-butylphenyl l-(trifluoromethyl)-2,2,2-trifluoroethyl carbonate Observations made 13 days after application (left column) m Observations made 23 days after application (right column) Pre-Ernergence Test Plant lb/A l0 lb/A Yellow Nutsedge (Cyperus exculentus L.) 7 5 Wild Oats (Avena fatua L.) 4 5 Jimsonweed (Datura slramam'um L.) l0 l0 Velvetleaf (Aubtilon lheophrasti Medic.) l0 l0 .lohnsongrass (Sorghum halepense Peri.) 5 2 Pigweed (Amaranlhus retroflexus L.) l0 l0 Mustard (Brassica kaber L. C. Wheeler Var.

pinnnnfida L. C. Wheeler) l0 10 Yellow Foxtail (Semria glnuca Beauv.) 8* 8* Barnyardgrass (Echinochloa crusgalli Beauv.) 6 4 Crabgrass (Digimria sanguinalis Soup.) 6 5 Buckwheat (Polygonum eonvolvulus L.) 6 7 Morning Glory (mixture of lpomoea purpurea Roth and Ipomaea hederacea .lacq.) 10 i0 Untreated Controls Normal Normal 2 Possible bird damage EXAMPLE XLl Test Compound: 2,4'-Dinitro-6'-sec-butylphenyl l-(trifluoromethyl)-2,2,2-trifluoroethyl carbonate Observations made 12 days after application Post- Test Plant Emergence l0 lb./A Yellow Nutsedge (Cyperur esculentus L.) 6 Wild Oats (Avena fatua L.) 6 Jirnsonweed (Darura stramonium L.) 10 Velvetleaf (Abutilon theophrasti Medic.) l0 .lohnsongrass (Sorghum halepense Pets.) 0 Mustard (Brassica kaber L. C. Wheeler Var. I

pinnanfida L. C. Wheeler) 10 Yellow Foxtail (Setaria glauca Beauv.) 2 4O Barnyardgrass (Echinochlaa crusgal'li Beauv.) 4 Buckwheat (Polyganum convolvulus L.) 10 Morning Glory (mixture of Ipomoea purpurea Roth and Ipomoea hedemcea Jacq.) 6 Red Kidney Bean (Phaseolus vulgaris L.) l Untreated Controls Normal EXAMPLE XLll Test Compound: 2',4-Dinitrophenyl 2,2,3,3-tetrafluoropropyl carbonate Observations made 13 days after application (left column) Observations made 23 days after application (right column) Pre-Emergence Test Plant l0 lb/A l0 lb/A Yellow Nutsedge (Cyperus esculemus L.) 0 0 Wild Oats (Avena form: L.) 0 0 .limsonweed (Datum stramom'um L.) 4 U Velvetleaf (Aburilon lheophmsti Medic.) 2 0 .lohnsongrass (Sorghum halepense Pers.) 0 0 6O Pigweed (Amaranthus retroflexus L.) 5 0 Mustard (Brassica kaber L. C. Wheeler Var.

. pirmnliflda L. C. Wheeler) 5 0 Yellow Foxtail (Setaria glnuaa Beauv.) 7* O Barnyardgrass (Echinochlon crusgalli Beauv.) 0 O Crabgrass (Digilaria sanguinalis Scop.) O 0 Buckwheat (Polygonum convolvulus L.) O O Morning Glory (mixture of lpomoea purpurea Roth and Ipomoea hederacea Jacq.) 0 0 Untreated Controls Possible bird damage. Normal Normal 36 EXAMPLE xun Test Compound: 2,4'-Dinitrophenyl 2,2,3,3,-tetrafluoropropyl carbonate Observations made 12 days after application EXAMPLE XLlV Test Compound: 2',6-Dinitrophenyl 2,2,3 ,3-tetrafluoropropyl carbonate Observations made 13 days after application (left column) Observations made 23 days after application (right column) Pre-Emergence lb/A l 0 lb/A Test Plant Yellow Nutsedge (Cyperus esculentur L.) Wild Oats (Avena fatua L.) .limsonweed (Datum :lramonium L.) Velvetleaf (Abun'lon theophrasti Medic.) .lohnsongrass (Sorghum halepem'e Pet's.) Pigweed (Amaranthu: retroflexus L.) Mustard (Brassica kaber L. C. Wheeler Var.

pinnaufda L. C. Wheeler) Yellow Foxtail (Serari'a glauca Beauv.) Bamyardgrass (Echinochloa crusgalli Beauv.) Crabgrass (Digilaria sanguinalis Scop.) Buckwheat (Polygonum convolvulus L.) Morning Glory (mixture of lpomoea purpurea Roth and lpamoea hederacea Jacq.) Untreated Controls Normal Norm EXAMPLE XLV.

Test Compound: 2',6-Dinitrophenyl 2,2,3,3-tetrafluoropropyl carbonate Observations made l2 days after application Post- Test Plant Emergence l0 lb/A. Yellow Nutsedge (Cyperus esculemus L.) 0 Wild Oats (Avena falua L.) 0 Jimsonweed (Datum stramomum L.) 10 Velvetleaf (Abutilon theophrasli Medic.) 3 Johnsongrass (Sorghum halepense Pers.) 0 Mustard (Bmssim kaber L. C. Wheeler Var.

pinnanjida L. C. Wheeler) 10 Yellow Foxtail (Semrta glauca Beauv.) 0 Barnyardgrass (Echinochloa crurgalli Beauv.) 0 Buckwheat (Polygonum convolvulus L.) 9 Morning Glory (mixture of lpomoea purpurea Roth and Ipamoea hederacea .lacq.) 3 Red Kidney Bean (Phmteolus vulgaris L.) 0 Untreated Controls Normal EXAMPLE XLVI Test Compound: 2',4'-Dinitro-6-sec-butylphenyl Z-fluoroethyl carbonate Observations made 13 days after application (left column) Observations made 23 days after application (right column) Untreated Controls Possible bird damage. Normal Normal EXAMPLE XLVII Test Compound: 2',4-Dinitro-6-sec-butylphenyl Z-fluoroethyl carbonate Observations made 12 days after application Post- Test Plant Emergence l lb./A Yellow Nutsedge (Cyperus esculenlu: L.) 0 Wild Oats (Avzna form: L.) 3 Jimsonweed (Darura stramonium L.) 10 Velvetleaf (Abutilon Iheophrasli Medic.) 4 Johnsongrass (Sorghum halepense Pers.) 0 Mustard (Brassica kaber L. C. Wheeler Var.

pinnatifida L. C. Wheeler) 10 Yellow Foxtail (Seraria glauca Beauv.) 0 Barnyardgrass (Echinochloa crusgalli Beauv.) 3 Buckwheat (Polygonum convalvulu: L.) l0 Morning Glory (mixture of Ipomoea purpurea Roth and Ipomoea hederacea .lacq.) 4 Red Kidney Bean (Phaseolus vulgaris L.) 0 Untreated Controls Normal EXAMPLE XLVlll Test Compound: 2',4'-Dinitro-6-tert-butylphenyl 2,2,3,3-tetrafluoropropyl carbonate Observations made 13 days after application (left column) Observations made 23 days after application (right column) Pro-Emergence Test Plant 10 lb/A l0 lb/A Yellow Nutsedge (Cyperus esculemus L.) 0 0 Wild Oats (Avena farua L.) 3 3 .limsonweed (Dalura rtramonium L.) l0 l0 Velvetleaf (Abutilon lheophrarti Medic.) 9 8 Johnsongrass (Sorghum halepense Pets.) 2 O Pigweed (Amaramhu: retroflexus L.) l0 l0 Mustard (Brassica kaber L. C. Wheeler Var.

pinnalzfida L. C. Wheeler) l0 [0 Yellow Foxtail (Selaria glauca Beauv.) 6* 6* Barnyardgrass (Echinochloa crusgalli Beauv.) 7 4 Crabgrass (Digitaria sanguinalis Scop.) 6 3 Buckwheat (Polygonum convolvulus L.) 7 10 Morning Glory (mixture of Ipomoea purpurea Roth and Ipomaea hederacea Jacq.) 9 l0 Untreated Controls Possible bird damage. Normal Normal EXAMPLE XLIX Test Compound: 2',4-Dinitro-6'-tert-butylphenyl 2,2,3,3-tetrafluoropropyl carbonate Observations made 12 days after application Post- Test Plant Emergence Yellow Nutsedgc (Cyperus esculenlux L.) 0 Wild Oats (Avena fatua L.) O .limsonwecd (Dalura slramonium L.) l() Velvetleaf (Abulilon Iheophrusli Medic.)

Johnsongrass (Sorghum halepenxe Pers.) 1 Mustard (Brassica kaber L. C. Wheeler Var.

pinnaulfida L. C. Wheeler) Yellow Foxtail (Seraria glauca Beauv.) 0 Barnyardgrass (Echinorhlva crusgalli Beauv.) O

Buckwheat (Polygonum convolvulus L.) 10 Morning Glory (mixture of Ipomoea purpurea Roth and lpomoea hea'eracea Jacq.) 0 Red Kidney Bean (Phaseolus vulgaris L.) 0 Untreated Controls Normal EXAMPLE L Test Compound: 2',4-Dinitro-6-sec-butylphenyl l H, l H.7H-dodecafluoroheptyl carbonate Observations made 13 days after application (left column) Observations made 23 days after application (right column) Pre-Emergence Test Plant 10 lb./A l0 lb/A Yellow Nutsedge (Cyperus esculentus L.) 0 0 Wild Oats (Avena fatua L.) O O Jimsonweed (Datura :tramonium L.) 2 O Velvetleaf (Aburilon lheophrasn Medic.) 7 0 Johnsongrass (Sorghum halepense Pers.) O O Pigweed (Amaranlhus retraflexus L.) 3 0 Mustard (Brasrica kaber L. C. Wheeler Var.

pinnalrfida L. C. Wheeler) 1 0 Yellow Foxtail (Selaria glauca Beauv.) 0 O Barnyardgrass (Echinochloa crusgalli Beauv.) O 0 Crabgrass (Digimria sanguinalis Seop.) 0 0 Buckwheat (Polygonum convulvulus L.) 0 0 Morning Glory (mixture of lpomoea purpurea Roth and lpomoea hedemcea Jacq.) 0 0 Untreated Controls Normal Normal EXAMPLE Ll Test Compound: 2,4'-Dinitro-6-sec-butylphenyl 1H,1H,7H-dodecafluoroheptyl carbonate Observations made 12 days after application Morning Glory (mixture of [pomoea purpurea Roth and lpomoea hederacea Jacq.) 2 Red Kidney Bean (Phaseolus vulgaris L.) l Untreated Controls Normal EXAMPLE Ll(a) Test Compound: 2,4-Dinitro-6-cyclohexylphenyl 2-fluoroethyl carbonate Pro-Emergence Observations made 13 days after application Post-Emergence Observations made 13 days after application Pre- Emergence l0 lb./A

Post- Emergence 10 lb./A

Test Plant Yellow Nutsedge (Cyperus esculenlus L.) Wild Oats (Avena fatua L.) Jimsonweed (Datum .rlramonium L.) Velvetleaf (Abutilan theaphrasti Medic.) Johnsongrass (Sorghum halepense Pers.) Pigweed (Amaranthus relroflexu: L.) Mustard (Brassica kaber L. C. Wheeler Var.

pinnatllfida L. C. Wheeler) Yellow Foxtail (Setaria glauca Beauv.) Barnyardgrass (Echinochloa crusgalli Beauv.) Crabgrass (Digitaria sanguinalis Scop.) Buckwheat (Polygonum canvolvulus L.) Morning Glory (mixture of Ipomaea purpureu Roth and Ipumoea hederacea Jacq.) Canada Thistle (Cirsium arvense [L.] Scop.) Cotton (Gossypium hirsutum L.) Untreated Controls roaooo J -wwuo E.o-oolooulooooo Normal Norm 

2. The compounds of claim 1 wherein R contains up to 8 carbon atoms.
 3. The compound of claim 2 wherein the value of k is
 2. 4. The compound of claim 2 wherein R is lower alkyl containing from 1 to 4 carbon atoms.
 5. The compound of claim 4 wherein R is secondary butyl.
 6. The compound of claim 2 wherein R is lower cycloalkyl containng from 5 to 8 carbon atoms.
 7. The compound of claim 6 wherein R is cyclohexyl.
 8. The compound of claim 2 wherein the value of x is
 2. 9. The compound of claim 8 wherein the two nitro groups are located in the 2'',4'' -positions and wherein R is located in the 6'' -position.
 10. The compound of claim 9 wherein R is secondary butyl or cyclohexyl.
 11. The compound of claim 1 which is represented by the structural formula:
 12. The compound of claim 11 wherein: a. the value of x is 2; b. the nitro groups are located in the 2'',4'' -positions; and c. R is located in the 6'' -position.
 13. The compound of claim 12 wherein R is secondary butyl or cyclohexyl.
 14. The compound of claim 1 which is represented by the structural formula:
 16. The compound of claim 15 wherein R is secondary butyl or cyclohexyl.
 17. The compound of claim 1 which is represented by the structural formula:
 18. The compound of claim 17 wherein: a. the value of x is 2; b. the nitro groups are located in the 2'',4'' -positions; and c. R is located in the 6'' -position.
 19. The compound of claim 18 wherein R is secondary butyl or cyclohexyl.
 20. The compound of claim 1 which is 2'',4'' -dinitro-6'' -sec-butylphenyl 2,2,2-trifluoroethyl carbonate.
 21. The compound of claim 1 which is 2'',4'' -dinitro-6'' -sec-butylphenyl 2,2,3,3-tetrafluoropropyl carbonate.
 21. The compound of claim 14 wherein: a. the value of x is 2; b. the nitro groups are located in the 2'',4'' -positions; and c. R is located in the 6'' -position.
 22. The compound of claim 1 which is 2'',4'' -dinitro-6'' -cyclohexylphenyl 2,2,3,3-tetrafluoropropyl carbonate.
 23. The compound of claim 1 which is 2'',4'' -dinitro-6'' -methylphenyl 2,2,3,3-tetrafluoropropyl car-bonate.
 24. The compound of claim 1 which is 2'',4'' -dinitro-6'' -sec-butylphenyl 1H,1H,7H-dodecafluoroheptyl carbonate.
 25. The compound of claim 1 which is 2'',4'' -dinitro-6'' -sec-butylphenyl 1H,1H,11H-eicosafluoroundecyl carbonate.
 26. The compound of claim 1 which is 2'',4'' -dinitro-6'' -sec-butylphenyl 1-(trifluoromethyl)-2,2,2-trifluoroethyl carbonate.
 27. The compound of claim 1 which is 2'',4'' -dinitrophenyl 2,2,3, 3-tetrafluoropropyl carbonate.
 28. The compound of claim 1 which is 2'',6'' -dinitrophenyl 2,2,3, 3-tetrafluoropropyl carbonate.
 29. The compound of claim 1 which is 2'',4'' -dinitro-6'' -sec-butylphenyl 2-fluoroethyl carbonate.
 30. The compound of claim 1 which is 2'',4'' -dinitro-6'' -tert-butylphenyl 2,2,3,3-tetrafluoropropyl carbontae.
 31. The compound of calim 1 which is 2'',4'' -dinitro-6'' -cyclohexylphenyl 2-fluoroethyl carbnate.
 32. The compound of claim 1 which is 2'',4'' -dinitro-6'' -cyclohexylphenyl 1-(trifluoromethyl)-2,2,2-trifluoroethyl carbonate.
 33. The compound of claim 1 which is 2'',4'' -dinitro-6'' -cyclohexylphenyl 1H,1H,7H-dodecafluoroheptyl carbonate.
 34. The compound of claim 1 which is 2'',4'' -dinitro-6'' -cyclohexylphenyl 1H,1H,11H-eiscosafluoroundecyl carbonate. 